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 Electrochemical and Solid-State Letters, 7 共8兲 A231-A234 共2004兲 A231
0013-4651/2004/7共8兲/A231/4/$7.00 © The Electrochemical Society, Inc.

Miniature 250 ␮m Thick Fuel Cell with Monolithically

Fabricated Silicon Electrodes
Masanori Hayase,*,z Takahiko Kawase, and Takeshi Hatsuzawa
Precision and Intelligence Laboratory, Tokyo Institute of Technology, Yokohama, Kanagawa 226-8503, Japan

A fabrication technique of miniature fuel cell electrodes was developed from Si wafers. The fuel channels, porous layer, and
catalyst layer were formed in the Si wafer. The fuel channels were fabricated by photolithographic patterning and subsequent wet
etching on the Si. The porous layer was formed by anodization of Si from the polymer electrolyte membrane side through the
bottom of the fuel channels. Catalyst metals were deposited inside the porous layer by wet plating. The two electrodes were
hot-pressed with a Nafion 112 sheet. Open-circuit voltage of 840 mV and maximum power density of 1.5 mW/cm2 were observed
by hydrogen feed.
© 2004 The Electrochemical Society. 关DOI: 10.1149/1.1756859兴 All rights reserved.

Manuscript submitted December 2, 2003; revised manuscript received January 12, 2004. Available electronically May 25, 2004.

The increasing interest for portable electronic systems drives the
research toward integrated regenerating power sources with small
dimensions and miniaturized fuel cells are attractive. The microfab-
rication technology of Si is an important tool to reduce the fuel cell
structure to micrometer sizes and have been employed by several
research groups.1-11 Those miniaturized fuel cells using various de-
grees of microfabrication techniques have been reported. Lee et al.1
created flowfields on Si substrate and formed hydrogen feed fuel cell
array on a Si wafer. Kelley et al.4 created catalyst layer supporter on
a Si chip and demonstrated that the miniaturized direct methanol
fuel cell 共DMFC兲 has almost same performance as state-of-the-art
larger fuel cells. However, those miniaturized fuel cells uses con-
ventional catalyst layers, in which Pt/Ru on activated carbon is
splayed on the gold sputter deposited silicon electrodes or conven-
tional membrane electrode assembly 共MEA兲 is used, and treating
powders such as activated carbon is not suitable for silicon batch
fabrication process. To adapt the construction process to more Si
processing steps, various approaches have been tried. In those stud-
ies, catalyst metals were deposited by physical vapor deposition
共PVD兲 on porous layers formed by photolithographic patterning or
anodization of Si.5-8 Generally, it is difficult to deposit materials
inside a porous layer by PVD and the catalyst deposits only on the
surface of the porous layer and the performance of the catalyst will
be poor. Therefore, a different approach to forming a catalyst layer
should be developed. Recently, D’Ariggo et al.9 proposed a novel
Si-based electrode fabrication technique, although the power genera-
tion is not reported yet. In this technique, the fuel channels were
formed inside the Si substrate by depositing an epitaxial Si layer
after wet etching of a Si substrate, then the deposited epitaxial Si
layer was anodized and the porous Si layer was obtained. Pt and Ru
were electrodeposited into the porous layer and the catalyst layer
was formed. Generally, resistivity of porous Si is high and it has
been supposed to be difficult to use a porous Si layer as a catalyst
support layer. However, porous Si has a large surface area up to
1700 m2/cm3 which is comparable with that of activated carbon12
and porous Si is attractive if it works as a catalyst support layer,
because fabrication of porous Si is easy and suitable for the batch Si
process. Our approach is close to the one by D’Arrigo and we pro-
pose a more simple structure of the electrode and a simple fabrica-
tion method.
Figure 1 shows the structure of our miniaturized fuel cell. Fuel
channels, fuel diffusion layer, and the catalyst support layer are
formed on the Si wafer without addition of other substances. A
porous Si layer is formed from the polymer electrolyte membrane
共PEM兲 side through the bottom of the fuel channels and a simple
cell structure is realized. Highly doped low resistivity Si is used and
the Si wafer itself is expected to work as a current collector. Thick-
* Electrochemical Society Active Member.
z
E-mail: hayase.masanori@pi.titech.ac.jp
ness of the Si wafer is 100 ␮m and the total thickness of the cell is
less than 300 ␮m. In this paper, we describe the fabrication proce-
dure of this fuel cell and preliminary experimental results of power
generation.
Experimental
Fuel channels.—Si electrodes were prepared using usual micro-
fabrication techniques. The first step was to spin-coat photoresist on
具100典 oriented 100 ␮m thick double-side mirror polished Si wafer
which has 500 nm thick thermal oxide films on both sides. For the
substrate, n-type Si was used because of the slow wet etching rate of
p-type Si. Because the Si substrate is expected to work as a current
collector, the lowest resistivity Si wafer among commercially avail-
able products 共supplied by Friend Science Inc., Japan兲 was chosen
and its resistivity was 0.001 ⍀ cm.
Next, using photolithographic patterning and subsequent wet
etching, the thermal oxide film on the Si wafer was patterned with
150 ␮m pitch stripes. By etching the exposed silicon in 15% tetram-
ethylamonium hydride 共TMAH兲 solution, fuel channels of 80-90
␮m depth were formed. Then the thermal oxide films of both sides
were etched in a dilute HF solution.
Porous Si layer.—Si becomes porous by anodization in a con-
centrated HF solution and this technique was used for the formation
of the porous layer on the electrodes. The morphology of porous Si
depends largely on the current density of anodization and the doping
ratio of the Si wafer. To find proper conditions, the anodization of
the highly doped Si wafer was performed with several current den-
sities. The composition of HF solution was HF (46%):ethanol
⫽ 1:1 共volume兲. A porous Si layer was obtained stably around 100
mA/cm2 and 100 mA/cm2 was chosen for the anodization process.
After the fuel channel formation, a Cu layer about 100 nm thick
was deposited by sputtering for good conductivity and the contact
pins were used for the current supply to the Si wafer from a poten-
tiostat. The Cu layer was removed after catalyst deposition by im-
mersing the chip in 40 wt% FeCl2 solution at 313 K for 3-5 min.
The anodization was performed from the PEM side of the Si wafer
until the porous layer reached the bottom of the fuel channels. Al-
though potential variation was observed during anodization using Pt
wire as a reference electrode, we could find no sign when the porous
layer reached the bottom of the fuel channels. Excess anodization
damages the porous layer especially around the bottom of the fuel
channels and strict time control of the anodization was required. The
depth of the trench varied up to a few micrometers even though
close attention was paid in the etching process. The growth rate of
the porous layer was about 45 nm/s and it varied by a small differ-
ence of the HF concentration or other conditions. Therefore, the
time of anodization was determined empirically by observing the
results with the same lot of trench-formed chips and the typical time
for the anodization was 5-6 min.
A232 Electrochemical and Solid-State Letters, 7 共8兲 A231-A234 共2004兲
Figure 1. Schematic view of the miniature fuel cell design. PEM sheet is
hot-pressed with monolithically fabricated Si electrodes. Catalyst metals are
supported by porous Si formed by anodization.
Figure 2 shows an example of the porous layer which was
formed from the PEM side of the Si wafer through the bottom of the
fuel channel. A uniform porous layer was obtained by anodization.
Although clear images of the pore morphology could not be ob-
tained, a similar feature reported by Lehman,12,13 in which there are
straight main pores of 10-100 nm diameter with many branches, was
supposed to be formed from the PEM side to the bottom of the fuel
channel by our vague scanning electron microscopy 共SEM兲 obser-
vations.
Catalyst layer.—Sputtering was employed in some studies to
deposit catalyst metals on the porous layer. The sputtering can
deposit catalyst metals only on the surface of the porous layer
and the performance of the catalyst layer is supposed to be poor.
Kelley and D’Arrigo employed electrodeposition and we tried to
deposit catalyst metals into the porous Si layer using a plating bath
of the same composition,4,9 1.0 M H2 SO4 ⫹ 16 mM H2 PtCl6
⫹ 8 mM K2 RuCl5 . However, energy dispersive X-ray spectros-
copy analysis 共EDS, JEOL JED-2200兲 showed that catalyst metals
deposited mainly on the surface and little deposition could be ob-
served inside the porous Si layer even by pulse plating, for instance
10 mA/cm2 was applied for 0.1 s following 0 mA/cm2 for 0.9 s until
the total applied charge reached 1 C/cm2. Various conditions were
tested and deposited metal often formed films on the porous surface
and peeled off from the porous Si layer.
Our EDS analysis showed a high oxygen signal in the porous Si
layer after electrodeposition. Si is a moderate reducing agent and it
reduces catalyst metal ions and simultaneously forms silicon dioxide
Figure 2. Cross-sectional view around the fuel channel bottom. Porous Si
layer formed from PEM side to the bottom of the fuel channel can be ob-
served. Strict time control of the anodization is required, because excess
anodization damages the porous Si layer.
Figure 3. Cross-sectional view of the catalyst metals deposited porous Si
layer. White lines show the detected signals of the catalyst metals obtained
by EDS analysis.
on bare Si, that is supposed to inhibit further electrodeposition.14 To
eliminate the silicon dioxide, dilute HF was added to the plating
bath and the deposition of catalyst metals was initiated. The addition
of HF removes silicon dioxide and prompts the reduction of catalyst
metal ions by increased bare Si surface.15-17 It was also observed
that Pt and Ru deposition occurred without applying electric current
when the dilute HF was added into the plating bath. Therefore,
electroless deposition occurs simultaneously with electrodeposition
and the amount of deposited catalyst metals is unable to be esti-
mated from the applied charge. Figure 3 shows an example of the
catalyst deposited porous Si layer using 1.0 M H2 SO4
⫹ 10 mM H2 PtCl6 ⫹ 5 mM K2 RuCl5 ⫹ 50 mM HF plating bath
at 293 K. Deposition was performed for 5 min applying 1 Hz pulse
current of 5 mA/cm2 for 0.2 s following 0 mA/cm2 for 0.8 s. The
white lines in Fig. 3 show the EDS intensity of Pt and Ru integrated
along the y direction. A strong EDS signal of the catalyst metals was
obtained inside the porous Si layer until a depth of 10 ␮m. Slight
nonuniformity due to the fuel channel was observed, but it can be
said that good catalyst deposition was obtained by the plating for
this preliminary experiment. The addition of dilute HF enhanced
catalyst metals deposition inside the porous layer and this method
was used for the formation of the catalyst layer.
Cell assembly.—Two Si electrodes were hot-pressed onto either
side of a Nafion 112 membrane. The miniature cells were assembled
by placing a piece of Nafion 112 sheet with Nafion 5% solution as
an adhesive between a catalyzed Si electrodes aligning edges of the
chips. The assembly was hot-pressed at approximately 0.05 MPa
and 443 K for 30 min and was then cooled to room temperature.
Figure 4 shows the assembled cell. The cell was set into an alumi-
num casing as shown in Fig. 5, which feeds the fuel to the fuel
channel and collects current from the cell.
Fuel cell testing.—The fuel cell testing was performed in a tem-
perature controlled chamber. Fuel and air supply lines were con-
nected to the aluminum casing. As shown in Fig. 5, fuels were fed
from the inlet hollow into the edge of the fuel channels and passes
through the channels on Si electrodes to the outlet hollow. Clamping
pressure was adjusted by the spring.
To humidify the PEM, hydrogen gas was passed through water
contained in a tank heated at 353 K and was then cooled to the
testing temperature in the feed line. No humidifying was performed
to the air feed. Current vs. voltage was measured by a potentiostat
共Hokuto Denko, HABF501兲 with scanning the cell potential at 5
mV/s.
 Electrochemical and Solid-State Letters, 7 共8兲 A231-A234 共2004兲
Figure 4. A preliminary prototype of the miniature 250 ␮m fuel cell with Si
electrodes. Nafion 112 sheet is hot-pressed between the two electrodes. Fuel
channels are formed in 5 ⫻ 5 mm area.
Results and Discussion
The design of the electrodes was devised to realize a simple
electrode fabrication process for miniature fuel cells that was highly
adapted to silicon microfabrication techniques. Other works of simi-
lar objective, that attempted to develop an alternative catalyst layer
to the carbon based one, have never succeeded in obtaining high
performance. The high resistivity of porous Si has hindered attempts
to use the porous Si directly as a catalyst support layer and current
collector. The proposed catalyst layer was fabricated in the highly
doped porous Si layer anodized at relatively high current density and
the porous Si was supposed to be still conductive. Beside there are
some reports that the resistivity decreases with humid air or metha-
nol vapor.18,19 Therefore, the porous Si layer was expected to work
as a catalyst support layer in the preliminary design and further
development of the cell design by thinning porous layer can relieve
the resistivity concerns.
The fuel cell testing was performed by feeding hydrogen gas or
dilute methanol solution to the cathode and air to the anode. Figure
6 shows the fuel cell polarization curves taken at two different tem-
peratures with hydrogen gas feed. About 20 cm3/min of hydrogen
gas and air were fed to the cell at ambient pressure. Varying the flow
rate of the fuel gases did not affect the performance at this testing
very much. Rather larger flow rate of the fuel gases reduced the
current density. This may indicate that larger gas flow dried the PEM
or the porous Si layer and the resistivity of the PEM or the porous Si
Figure 5. Aluminum casing for the miniature thin fuel cell testing. Gener-
ated current is collected by this casing from the silicon electrode by direct
contact. The cells are put between the two casings as shown in right figure.
Fuel is supplied to the fuel channels from the right hole and is discharged
from the left hole on the stage.
A233
Figure 6. Current-voltage characteristics of the miniature fuel cell with hy-
drogen gas feed. Peak power of 1.5 mW/cm2 is observed at 353 K.
layer increased. The silicon electrode is brittle and a large clamping
pressure was not applied. The pressure was varied from 0.1 to 0.3
MPa and no obvious change was observed. This may suggest that no
large clamping pressure is necessary because the electrodes are
monolithic and no improvement of the conductivity between a cata-
lyst layer and a separator by high pressure is expected. As expected,
cell performance improved at higher temperature. If the resistivity of
the porous Si layer or Si substrate dominated the performance, a
polarization curve would show a linear line. The polarization curves
obtained drew gentle curves and this may suggest that the cell per-
formance was dominated by the catalyst performance. Methanol so-
lution feed was also examined. 1 cm3/min of 1 M methanol solution
was fed. The open-circuit voltage of 320 mV was obtained 3 min
after the fuel feed start and polarization was measured. Although 0.5
mA/cm2 was observed, the performance deteriorated significantly
and the cell became inactive, maybe due to the poor performance of
the catalyst and methanol cross over. 共See Fig. 7兲.
The obtained result showed the highest performance compared
with recent miniature fuel cells proposing new catalyst layer
structures,5-11 although it was far inferior to large fuel cells with
carbon-support based catalyst layers. The porous Si layer worked
successfully as a catalyst support layer and a current collector. The
amount of catalyst metal was unknown and there is much room for
improvement in the structure of the catalyst layer.
Figure 7. Current-voltage characteristics of the miniature fuel cell with 1 M
methanol solution feed.
A234 Electrochemical and Solid-State Letters, 7 共8兲 A231-A234 共2004兲
Conclusion
A 250 ␮m thick miniature fuel cell design was proposed and a
prototype was produced. The Si electrodes had etched fuel channels
and a porous Si layer which was formed by anodization from the
PEM side through the bottom of the fuel channels. Catalyst metals
were deposited inside the porous Si layer by the wet plating process,
in which the deposition of catalyst metals was enhanced by addition
of dilute HF into the plating bath. Power generation of the miniature
fuel cell was verified and the highest performance was shown com-
pared with recent miniature fuel cells proposing catalyst layer struc-
tures without a conventional carbon-support catalyst layer. It was
verified that the porous Si layer can work as a catalyst support layer
and further study will be performed.
Acknowledgment
This study was supported by industrial technology research grant
program in ’01A35005c from New Energy and Industrial Technol-
ogy Development Organization 共NEDO兲 of Japan. The authors
thank Professor Yohtaro Yamazaki of Tokyo Institute of Technology
for useful discussions.
Tokyo Institute of Technology assisted in meeting the publication costs of
this article.
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